JPH1149916A - Rapid-curing two-package adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having rapid curability, a high final bonding strength, storage stability and mechanical stability by preparing a first package comprising an aqueous solution containing a vinyl alcohol polymer having phenyl-bonded amino groups and a second package comprising a water-soluble oxidizing agent. SOLUTION: The vinyl alcohol polymer used in the first package is represented by formula I or II (wherein R<1> to R<5> are each H or a hydrocarbon group which may have an 8C or lower substituent; A is a divalent hydrocarbon group or a divalent hydrocarbon group containing at least one kind of N, O or S atoms; and is a monovalent group having a phenyl-bonded amino group) and has a content of structural units X of 0.01-30 mol.%. The vinyl alcohol polymer has a viscosity-average degree of polymerization of 50-10,000 and a degree of saponification of 50 mol.% or above. The water-soluble oxidizing agent is exemplified by ammonium persulfate and is used in the form of a 1-50% aqueous solution. If necessary, this composition may contain a polyepoxy compound, an aldehyde compound or a polyisocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a two-part adhesive composition and an adhesive method using the same. More specifically, the present invention relates to a two-part adhesive composition having a particularly high initial curing rate and excellent workability during bonding.

[0002]

2. Description of the Related Art Recently, in the wood products industry, it has been studied to make a production process continuous by a conveyor system. Therefore, an adhesive having a high bonding speed has been demanded. For this purpose, cyanoacrylate-based instant adhesives have been proposed, but are extremely expensive and not practical. Further, a two-liquid separation coating type adhesive composition using a urea resin-based adhesive as a first liquid, and mixing a strong acid such as phosphoric acid with an aqueous solution of a polymer compound such as polyvinyl alcohol (PVA) as a second liquid. Has been proposed. However, since this adhesive composition uses a strong acid, there is a disadvantage that the resin component contained in the adhesive is easily aged, and furthermore, the adherend is easily stained or deteriorated.

An aqueous solution of a polymer compound having an imide group in the molecule (isobutylene-maleic anhydride copolymer) or a synthetic resin emulsion containing the polymer compound is used as a first liquid, and an aqueous solution of an aldehyde compound is used as a first liquid. 2. Description of the Related Art A two-component, separate-coating-type adhesive composition having two components is known (JP-A-56-90867). However, this adhesive composition has a disadvantage of low adhesive strength. Further, an aqueous solution and / or aqueous emulsion of a polymer compound having an acetoacetyl group in a molecule is used as a first liquid, and a liquid containing an aldehyde compound or a hydrazine compound is used as a second liquid.
An adhesive composition of a liquid separation coating type is known (Japanese Patent Laid-Open No.
0-202176 and JP-A-61-78883.
No.). However, in this adhesive composition, the storage stability of the first liquid is poor, and there is a problem in reproducibility of the adhesive performance.

Further, JP-A-3-281683 discloses an aqueous solution of a polymer compound having a primary or secondary amino group in the molecule (polyamine) or a mixture of the polymer compound and a synthetic resin emulsion. There has been proposed a two-liquid separation coating adhesive composition in which an aldehyde compound is used as a first liquid and a second liquid is used. However, this adhesive composition has a problem that the storage stability of the first liquid is poor and the efficiency of crosslinking with the aldehyde compound is low, so that sufficient fast curability cannot be obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to develop a high initial adhesive strength by curing at room temperature in a short time, thereby making the bonding operation extremely difficult. An object of the present invention is to provide a two-part adhesive composition that can be performed smoothly with low energy cost and with good productivity. Further, the object of the present invention is to have excellent storage stability and mechanical stability together with the above-mentioned property of fast curing,
The components are unlikely to settle, separate, or agglomerate even if left unattended.Also, the components are unlikely to settle, separate, or agglomerate when subjected to the action of rocking, stirring, etc. during transportation or handling. Another object of the present invention is to provide a two-part adhesive composition which can maintain its adhesive performance in a good condition. Furthermore, an object of the present invention is to provide a compound having such excellent properties.
An object of the present invention is to provide a bonding method using a liquid adhesive composition.

[0006]

As a result of extensive studies by the present inventors to achieve the above object, an aqueous liquid containing a vinyl alcohol polymer having an amino group bonded to a phenyl group was used as a first liquid. When a two-part adhesive composition is prepared by using a liquid containing a water-soluble oxidizing agent as a second part, and bonding is performed using this two-part adhesive composition, in particular, the first part is applied on one side. When the second liquid is applied to another adhered surface and the adhered surfaces are brought into close contact with each other, a high initial adhesive strength can be obtained at room temperature in a short time (approximately after the adhered surfaces are adhered to each other). That the bonding operation can be carried out with good workability with good productivity and low energy consumption, and that the adherend obtained therefrom has a high final adhesive strength (bonding strength). (Approximately 24 hours or more after the adhesion between the contact surfaces) It was found to be current. Furthermore, the present inventors have found that such a two-part adhesive composition, when the first part and the second part are individually stored in a non-mixed state, the separation, sedimentation, aggregation, etc. of the components. It has been found that it is stable without generation, and that its adhesion performance is maintained without deterioration even after long-term storage. Furthermore, the present inventors, when using a liquid containing a water-soluble oxidizing agent as the second liquid in such a two-part adhesive composition, when at least one of the first liquid and the second liquid, a polyvalent epoxy compound, an aldehyde It has been found that when at least one compound selected from a compound and a polyvalent isocyanate compound is further contained, the final adhesive strength is further improved, and the present invention has been completed based on those findings.

That is, the present invention provides a two-part adhesive comprising a first liquid comprising an aqueous liquid containing a vinyl alcohol polymer having an amino group bonded to a phenyl group, and a second liquid containing a water-soluble oxidizing agent. A composition.

Further, the present invention provides the above two-part adhesive, wherein at least one of the first and second liquids further contains at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound. The compositions fall within the scope of the present invention.

Then, the present invention provides a method for applying a first liquid of any of the above two-part adhesive compositions to a first adherend surface,
A bonding method characterized in that a liquid is applied to a second adherend surface, and the two applied surfaces are brought into close contact with each other for adhesion.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, in the two-part adhesive composition of the present invention, a vinyl alcohol-based polymer having an amino group bonded to a phenyl group (hereinafter referred to as “aniline group-containing PV
A). In the present invention, any vinyl alcohol polymer having an amino group bonded to a phenyl group can be used as the aniline group-containing PVA. In that case, the aniline group-containing PVA
The type of the structural unit having an amino group bonded to the phenyl group in is not particularly limited. Specific examples thereof include PVA having the following structural unit represented by Chemical Formula 3 or Chemical Formula 4; PVA having an amino group bonded to a phenyl group obtained by acetalizing PVA with an aldehyde having an aromatic amino group; Examples include PVA having an acid vinyl unit, and among them, PVA having the following structural unit represented by Chemical formula 3 or Chemical formula 4 is most suitable.

[0011]

Embedded image

[0012]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms, and A is a divalent At least one hydrocarbon group or at least one nitrogen, oxygen or sulfur atom
Represents a divalent hydrocarbon group containing species, S represents a sulfur atom,
X represents a monovalent group containing an amino group bonded to a phenyl group. )

R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the structural unit represented by the above formula 3 or 4 may have a hydrogen atom or a substituent having 8 or less carbon atoms. There is no particular limitation as long as it is a hydrocarbon group, but R ¹ is a hydrogen atom,
² is a hydrogen atom or a methyl group, and R ³ , R ⁴ and R ⁵ are preferably a hydrogen atom or a hydrocarbon having 8 or less carbon atoms (preferably 6 or less carbon atoms). Note that R ³ and R ⁴ (or R ⁵ ) may form a ring. A in the structural unit represented by Chemical Formula 4 is a divalent hydrocarbon group or a nitrogen atom,
The structure is not particularly limited as long as it is a divalent hydrocarbon group containing at least one oxygen atom or sulfur atom, and examples thereof include-(CH2) n- (n = 1 to 10, preferably 1 to 8), −
CH2OCH2-, -OCH2-, -CONH-ph
-OCH2-, -CONHCH2-, -CONHCH2
OCH2-, -CONHCH2OCH2CH2-, -C
ONHCH2OCH2CH2CH2-, -CONHCH
2OCH2CH2CH2CH2-, -CONHCH2-
ph (CH3) 2-CH2- and the like. (Note that
ph means a phenyl group. X in the structural unit represented by Chemical Formula 3 or Chemical Formula 4 is not particularly limited as long as it is a monovalent group containing an amino group bonded to a phenyl group.
(1,2-), -ph-NH2 (1,3-), -ph-
NH2 (1,4-), -CH2-ph-NH2 (1,
2-), -CH2-ph-NH2 (1,3-), -C
H2-ph-NH2 (1,4-), -CH2 CH2
-Ph-NH2 (1,2-), -CH2CH2-ph
-NH2 (1,3-), -CH2CH2-ph-NH
2 (1,4-), -ph (CH3) -NH2 (1,
2,3-), -ph (CH3) -NH2 (1,2,4
-, -Ph (CH3) -NH2 (1,2,5-),-
ph (CH3) -NH2 (1,2,6-), -nph
-NH2 (1,2-), -nph-NH2 (1,4
-), -Nph-NH2 (1,8-) and the like.
(In addition, ph means a phenyl group, and nph means a naphthalene group.)

[0015] The content of the structural unit containing an amino group bonded to the phenyl group is 0.01 to 30 mol%, and there is no particular limitation on the distribution of the structural unit in the polymer. When the content of the structural unit is O. If the amount is less than 1 mol%, the effect of introduction is not sufficiently exhibited, and if it exceeds 30 mol%, a problem (eg, gelation) occurs in the storage stability of the water-resistant composition. A more preferred range for the content of the structural unit is 0.1.
02 to 20 mol%, and a particularly preferable range is 0.05 to 20 mol%.
１５15 mol%.

The viscosity average degree of polymerization (hereinafter abbreviated as degree of polymerization) and the degree of saponification of PVA are appropriately selected according to the purpose.
There is no particular limitation. The degree of polymerization is usually 50 to 1000
0, preferably 100-7000, more preferably 10
0 to 5000. The degree of saponification is at least 50 mol%, preferably at least 70 mol%. Saponification degree 50
If it is lower than mol%, the water solubility will decrease.

The content of the amino group bonded to the phenyl group in the aniline group-containing PVA is not particularly limited, and the application and usage of the adhesive composition, the type of the component contained in the first liquid and the second liquid, and the like. It can be appropriately selected according to various situations such as the amount and amount. Usually, PVA containing an aniline group
The proportion of the structural unit having an amino group bonded to a phenyl group is preferably about 0.1 to 30 mol%, more preferably 0.5 to 25 mol%, based on all the structural units constituting preferable. When the proportion of the structural unit having an amino group bonded to a phenyl group in the aniline group-containing PVA is less than 0.1 mol% or more than 30 mol%, the initial adhesive strength and the final adhesive strength may not be sufficiently high. .

The degree of polymerization of the aniline group-containing PVA is as follows:
The purpose of use of the adhesive composition, the type and amount of other components contained in the adhesive composition, may vary depending on the phase morphology of the adhesive composition, etc., usually, its polymerization degree is 100 or more It is preferable from the viewpoint of initial adhesive strength and final adhesive strength.
More preferably, it is 0-8000. The degree of saponification of the aniline group-containing PVA also varies depending on the various requirements as described above. In general, it is required that 50 mol% or more of the structural unit based on vinyl alcohol is saponified. Preferred from the point, 80 to 99.9 mol%
Is more preferably saponified. In addition, the aniline group-containing PVA may contain other structural units together with the structural unit based on vinyl alcohol and the structural unit having an amino group bonded to the phenyl group, as long as the effect of the present invention is not hindered. .

The method for producing the aniline group-containing PVA is not particularly limited and can be obtained by various methods. Examples thereof include: (1) an ethylenically unsaturated monomer having an amino group bonded to a phenyl group, After copolymerizing an ethylenically unsaturated monomer having a substituent capable of forming an amino group bonded to a phenyl group by decomposition, and vinyl acetate,
(2) After copolymerizing vinyl acetate with an unsaturated monomer having an epoxy group such as allyl glucidyl ether,
In the epoxy group of the side chain in the copolymer obtained thereby,
A method in which a mercaptan having an amino group bonded to a phenyl group is subjected to an addition reaction in the presence of a sodium hydroxide catalyst, followed by saponification; (3) a method having an amino group bonded to a phenyl group and reacting with a hydroxyl group of polyvinyl alcohol; A method in which a compound having a functional group is reacted with polyvinyl alcohol to introduce an amino group bonded to a phenyl group into the polyvinyl alcohol; (4) an amino group bonded to the phenyl group with respect to the polyvinyl alcohol having a mercapto group; A block copolymer comprising a polyvinyl alcohol block and a polymer block having an amino group bonded to a phenyl group by block polymerization of an ethylenically unsaturated monomer having the formula:

In the two-part adhesive composition of the present invention, the first part is an aqueous liquid containing at least aniline group-containing PVA and using water as a medium. It is desirable that the aqueous solution be capable of maintaining a stable aqueous liquid state without causing separation, sedimentation, aggregation, and the like. As a typical example of the first liquid used in the two-part adhesive composition of the present invention, (a) an aqueous liquid mainly composed of an aqueous aniline group-containing PVA solution [hereinafter referred to as “first (a) liquid” And (b) an aqueous liquid mainly comprising an aniline group-containing PVA and an organic polymer aqueous emulsion (an aqueous liquid obtained by mixing an aniline group-containing PVA directly or in an aqueous liquid with an organic polymer aqueous emulsion) [hereinafter, This is sometimes referred to as “first (b) liquid”].

Therefore, the above-mentioned first liquid preferably used as the first liquid in the two-part adhesive composition of the present invention.
The liquid (a) will be specifically described. The first liquid (a) preferably used as the first liquid in the two-part adhesive composition of the present invention is an aqueous liquid mainly composed of an aqueous solution of aniline group-containing PVA. The method for preparing the first liquid (a) is not particularly limited, and usually, the aniline group-containing P
It can be prepared by dissolving VA in water at a suitable temperature, preferably at a temperature of 50 to 100 ° C. The concentration of the aniline group-containing PVA in the first liquid (a) is 2
Although it can be adjusted according to the use of the liquid adhesive composition and the type and concentration of other components contained in the adhesive composition, it is generally possible to prepare an aqueous solution having a concentration of 5 to 20% by weight. It is preferable in terms of storage stability, handleability, adhesive performance, and the like. Further, the first liquid (a) may contain polyvinyl alcohol having no amino group, together with the aniline group-containing PVA, in an amount that does not impair the purpose.

Next, the first liquid (b) which is preferably used as the first liquid in the two-part adhesive composition of the present invention will be described. The first (b) liquid is an aniline group-containing PV
An aqueous liquid mainly consisting of A and an organic polymer aqueous emulsion. Generally, an aniline group-containing PVA is directly mixed with an organic polymer aqueous emulsion prepared in advance, or an aqueous solution of an aniline group-containing PVA is mixed. Can be obtained. As the organic polymer aqueous emulsion in that case, unsaturated monomers, for example, vinyl ester unsaturated monomers such as vinyl acetate,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
(Meth) such as 2-ethylhexyl (meth) acrylate
Acrylic acid alkyl ester, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid 2-
Acrylic unsaturated monomers such as hydroxyethyl, vinyl chloride, vinylidene chloride, halogen-containing unsaturated monomers such as vinyl bromide, styrene monomers, olefin monomers such as propylene, butadiene, isoprene, One or two or more diene monomers such as chloroprene are used in the same manner as in a normal emulsion polymerization reaction using the same emulsifier as that used in a normal emulsion polymerization to form a radical polymerization initiator. It is carried out by using and polymerizing. As the polymerization initiator at that time, for example, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide,
Azobisisobutyronitrile, persulfate (potassium, sodium or ammonium salt), t-butyl peracetate,
Redox catalysts such as t-butyl benzoate alone or the above compound and sodium sulfite, triethanolamine, Rongalit, L-ascorbic acid, tartaric acid and the like are used.

In the first liquid (b), the ratio between the organic polymer (organic polymer obtained by polymerization of the unsaturated monomer described above) and the aniline group-containing PVA is adjusted according to each situation. However, the ratio of the aniline group-containing PVA to 100 parts by weight of the organic polymer is preferably 0.1%.
By setting the amount to 5 to 300 parts by weight, more preferably 1 to 200 parts by weight, the first emulsion in the form of an emulsion having a high solid content and excellent storage stability and mechanical stability.
The liquid (b) is obtained, and the two-part adhesive composition of the present invention using the first liquid (b) is particularly excellent in initial adhesive strength.

Further, the first liquid (b) may contain polyvinyl alcohol having no aniline group together with aniline group-containing PVA in an amount not to impair the purpose. Also, in the first liquid (b), the dispersion concentration of the first liquid (b) and the initial concentration of the adhesive composition should be such that the total concentration of all the polymers in the aqueous liquid is about 20 to 70% by weight. It is preferable from the viewpoint of adhesive strength, final adhesive strength, handleability, adhesive workability, and the like.

In the two-part adhesive composition of the present invention, a liquid containing a water-soluble oxidizing agent is used as the second liquid together with the first liquid.

The water-soluble oxidizing agent used in the second liquid includes persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t -Butyl hydroperoxide, potassium bromate, t-butyl peracetate, t-butyl benzoate, and the like. One or more of these water-soluble oxidizing agents can be used. And, in the two-part adhesive composition of the present invention, the second liquid may have a water-soluble oxidizing agent dissolved in water, so that the handleability and the initial adhesive strength at the time of performing the bonding operation are improved. It is preferable from the viewpoint of improvement and the like, and it is usually preferable to use a water-soluble oxidizing agent in a state of a 1 to 50% aqueous solution.

In the two-part adhesive composition of the present invention, one or both of the second part and the first part are selected from a polyepoxy compound, an aldehyde compound and a polyisocyanate compound as required. It may contain at least one compound. In the two-part adhesive composition of the present invention, when at least one of the second part and the first part contains at least one compound selected from the group consisting of a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound, It is possible to further increase the final adhesive strength of the agent composition. In this case, the polyhydric epoxy compound can be easily mixed with the first liquid and / or the second liquid in the form of a solution and / or an emulsion, and the storage stability and mechanical stability of the first liquid and the second liquid can be improved.
Any polyepoxy compound can be used as long as it does not significantly impair the adhesive force or the like and exhibits a good crosslinking action when the first liquid and the second liquid are closely adhered or mixed at the time of adhesion. As such a polyvalent epoxy compound, for example, polyol epoxide of polyol is preferably used, and specific examples thereof include ethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether. Can be mentioned.

The aldehyde compound may be any compound having a substantially aldehyde group or an aldehyde compound which can be present as a hydrate thereof when dissolved or dispersed in water. Examples thereof include formaldehyde, acetaldehyde, propionaldehyde, and the like. Crotonaldehyde, benzaldehyde, glyoxal, malonaldehyde, fuchsindialdehyde, glutaraldehyde,
Vimerin dialdehyde, suberin dialdehyde, dialdehyde starch and the like can be mentioned.

The type of the polyvalent isocyanate compound is not particularly limited, and any compound can be used as long as it can be cured by reaction with aniline group-containing PVA in the first liquid. For example, tolylene diisocyanate (TDI) ), Hydrogenated TDI, trimethylolpropane-TDI adduct (for example, Desmodur L, manufactured by Bayer AG),
Triphenylmethane triisocyanate, methylenebisdiphenyl isocyanate (MDI), hydrogenated MDI,
Water-insoluble isocyanate compounds such as polymerized MDI, hexamethylene diisocyanate, xylylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, blocked products thereof, and polymethoxyethylene glycol or the like added to the water-insoluble isocyanate to disperse in water. (For example, manufactured by Nippon Polyurethane Co., Ltd .: trade name Coronate C-3)
053). The polyvalent isocyanate compound may be used in the liquid state as it is, or may be used by dissolving in a solvent that does not react with isocyanate, for example, a solvent having no active hydrogen atom such as dibutyl phthalate or xylene. It is preferable to use them. In the case of a water-dispersible polyvalent isocyanate compound, it may be used by dispersing it in water.

At least one compound selected from the group consisting of polyepoxy compounds, aldehyde compounds and polyisocyanate compounds may be used alone or in combination of two or more.

The amount of at least one compound selected from the group consisting of the polyepoxy compound, the aldehyde compound and the polyvalent isocyanate compound depends on the use of the adhesive composition and the type and amount of other components used in the adhesive composition. In the case where at least one compound selected from a polyhydric epoxy compound, an aldehyde compound and a polyvalent isocyanate compound is added only to one of the first liquid and the second liquid, or both are added. In this case, it is preferable that the amount be 1 to 200 parts by weight based on 100 parts by weight of the aniline group-containing PVA contained in the first liquid, from the viewpoint of the final adhesive strength of the adhesive composition, and 3 to 15 parts by weight.
More preferably, it is 0 parts by weight.

As apparent from the above description, the two-part adhesive composition of the present invention comprises: (1) the first part is the first part (a), and the second part is the water-soluble oxidizing agent. (2) a two-component adhesive composition, wherein the first component is the first component (b) and the second component is a component containing a water-soluble oxidizing agent; (3) The first liquid is the first liquid (a) or the first liquid (b), and the second liquid is at least one kind selected from a water-soluble oxidizing agent and a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound. A two-part adhesive composition which is a liquid containing a compound; (4) a first liquid containing at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound; First
(B) a two-part adhesive composition wherein the liquid is a liquid and the second liquid is a liquid containing a water-soluble oxidizing agent; (5) the first liquid is selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound (A) liquid or first liquid containing at least one compound
(B) a two-part adhesive composition, wherein the second part is a liquid and the second part is a liquid containing a water-soluble oxidizing agent and at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate compound; Such various embodiments of the two-part adhesive composition are included. And among the above-mentioned various aspects, those using the aspects (1) to (3) are preferable.

In the two-part adhesive composition of the present invention, the first part may contain a filler, if necessary, for the purpose of increasing the amount and strengthening. , Calcium carbonate, kaolin, baryta, wood flour, plant flour and the like, and one or more of them can be contained. Further, the first liquid may contain a plasticizer, a colorant, and other compounding agents as necessary. Further, the present invention relates to a two-component adhesive composition having a second composition.
The liquid may appropriately contain one or more of a colorant, a surfactant, a viscosity modifier, and the like, as needed, as long as the performance of the second liquid is not impaired.

In the two-part adhesive composition of the present invention, the ratio of the first part to the second part depends on the use and usage of the adhesive composition, the types of components contained in both parts, and the adherend. Although it may vary depending on the method of applying the adhesive liquid, the type of the adherend, etc., usually, the second liquid is preferably 0.2 to 150 parts by weight, more preferably 100 parts by weight of the first liquid, more preferably 1st liquid
It is preferable to use 100 parts by weight.

Before the two-part adhesive composition of the present invention is used in the bonding operation, the first liquid and the second liquid are separated from each other (non-mixed state) and put in a container or the like. Save,
It is distributed and sold. Then, in performing the bonding operation using the two-part adhesive composition of the present invention, the first part of the two-part adhesive composition is applied to the first surface to be adhered, and the second part is applied to the second part.
(2) a method in which both the application surfaces are brought into close contact with each other, and the adhesive composition is reacted and cured to adhere.
Liquid separation coating method), or a method of mixing the first liquid and the second liquid immediately before bonding and applying the mixed liquid to an adherend immediately to perform bonding. In the two-part adhesive composition, when the first and second parts are brought into contact with each other, the reaction curing usually proceeds rapidly even at room temperature. Therefore, the former two-part separation coating method is preferably used. When the two-component adhesive composition of the present invention is bonded by a two-component separation coating method, its properties such as its quick-curing property and high initial adhesive strength are sufficiently exhibited, resulting in extremely good workability. In addition, the bonding operation can be performed with high productivity in a short time with low energy cost. Therefore, the two-part adhesive composition of the present invention is particularly suitable as a two-part separate application type adhesive composition.

When the bonding operation is performed by the above-mentioned two-liquid separation coating method, the adhered surface coated with the first liquid and the coated surface coated with the second liquid are brought into close contact with each other, and then pressed and pressed. Since high initial adhesive strength is developed in a very short time (usually within 1 to 5 minutes), pressing and pressing can be released in a short time, shortening the working time, simplifying the working process,
It is possible to achieve simplification of the device, reduction of energy cost, and the like. Then, the adherend, which was able to obtain a sufficiently high adhesive strength by pressing and pressing, releases the pressed and pressed state, and is left and cured to obtain an adherend having a sufficiently high final adhesive strength. Can be obtained.
In the case of a conventional adhesive using water as a medium, a sufficient final adhesive strength cannot be generally obtained unless pressing and pressing for a long time at room temperature, but the two-part adhesive composition of the present invention is used. By using, the property of fast curing makes it possible to leave the press and press even for a short period of time, and to perform adhesion with sufficient final adhesive strength after curing, which is extremely useful in this respect.

In performing the bonding operation using the two-component adhesive composition of the present invention, the second liquid is applied to one of the surfaces to be adhered in advance, dried, and then the first liquid is applied to the other surface. The two-part adhesive composition of the present invention can be applied to woodworking work, etc., since the desired two-part adhesive composition can be applied to the surfaces to be adhered to each other and the two adhered surfaces can be adhered and adhered to each other to perform desired bonding. Systematization is possible.

When the two-component adhesive composition of the present invention is used to perform adhesion by a two-component separation coating method, the first component on the surface to be adhered is used.
The application amounts of the liquid and the second liquid are not particularly limited, and can be adjusted according to the type and state of the adherend, the contents of the components of the adhesive composition, and the like. The application amount of the first liquid is about 10 to 500 g / m ^2, and the application amount of the second liquid on the second adherend surface is about 5 to 100 g / m ² ,
It is preferable to bond both application surfaces in close contact because high adhesion strength can be obtained while effectively using the first and second liquids without waste.

When bonding is performed using the two-part adhesive composition of the present invention, a gelling reaction of the aniline group-containing PVA contained in the first part occurs due to the water-soluble oxidizing agent contained in the second part. The initial adhesive strength is improved. Further, when the first liquid and / or the second liquid contains at least one compound selected from a polyvalent epoxy compound, an aldehyde compound and a polyvalent isocyanate, a strong crosslinking reaction of the aniline group-containing PVA occurs, An adhesive film having excellent elasticity and water resistance is formed, and the final adhesive strength is significantly improved.

The two-part adhesive composition of the present invention can be used for various woody materials, for example, wood, materials such as chipboard and hardboard, woody materials such as slate board and silica board; melamine resin decorative material, bakelite And other plastic materials; paper materials such as corrugated paperboard and kraft paper; fabrics and other fiber products; and inorganic materials. In bonding the various materials described above using the two-component adhesive composition of the present invention, it can be used for both bonding between materials of the same type and bonding between different materials, particularly for bonding wood. Are suitable. However, of course, it is not limited thereto. Therefore, by using the two-part adhesive composition of the present invention,
Although it is not limited at all, for example, manufacturing and assembling of a flush panel, a laminated glue and the like, flattening and edge sticking, a tenon, a dowel, a tome, a sword, a squared wood, a box body, and other assembling and bonding work, The method can be carried out while saving energy because it is quick and labor-saving, and can bond well even at room temperature.

[0041]

EXAMPLES The present invention will now be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “%” and “parts” mean “% by weight” and “parts by weight”, respectively, unless otherwise specified.

<< Synthesis Example 1 >> [Synthesis of aniline group-containing PVA] (1) In a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 405 parts of vinyl acetate monomer, 11 parts of allyl glycidyl ether and 30 parts of methanol was charged, and nitrogen gas was bubbled for 15 minutes to degas. Separately, an initiator solution prepared by dissolving 4.5 parts of 2,2-azoisobutyronitrile in 15 parts of methanol was prepared, and nitrogen was replaced by bubbling with nitrogen gas. The temperature of the reactor was raised, and when the internal temperature reached 60 ° C., a separately adjusted initiator solution was added to initiate polymerization. Polymerization was carried out at 60 ° C. for 4 hours, and the polymerization was stopped by cooling. The solid content at this time was 54.
8%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure, and a methanol solution of a polyvinyl acetate copolymer (concentration 4
4.5%). A part of this methanol solution was put into ether to recover the polymer, which was purified by reprecipitation twice with acetone / ether, and then dried at 40 ° C. under reduced pressure. Proton NMR (“GSX-270” manufactured by JEOL Ltd.) was measured on the purified polymer using CDCl 3 as a solvent. As a result, polyvinyl acetate containing 2.1 mol% of allyl glycidyl ether units (epoxy groups) was obtained. It was a polymer.

(2) A methanol solution of the polymer having an epoxy group obtained in the above (1) (concentration: 44.5) was placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer.
%), And after bubbling with nitrogen gas for 15 minutes, a solution prepared by dissolving 8.0 parts of 2-aminothiophenol and 0.03 part of sodium hydroxide in 48 parts of methanol was charged. After reacting at 50 ° C. for 2 hours with stirring, the mixture was cooled to 40 ° C. and saponified by adding 40 parts of a 10% strength methanol solution of sodium hydroxide. 4
The mixture was allowed to stand at 0 ° C. for 5 hours, pulverized, neutralized by adding 8 parts of acetic acid, and then treated with methanol using a Soxhlet extractor.
After washing for at least 20 hours and drying at 60 ° C. for at least 20 hours, an aniline group-containing PVA was obtained. IR of PVA containing aniline group
And proton NMR (d6-DMSO), the epoxy group had completely disappeared and 2.1 mol%
Was confirmed to have an aniline group, and the vinyl alcohol content was 97.0 mol%. The degree of polymerization of the aniline group-containing PVA was 900 (hereinafter, the aniline group-containing PVA thus obtained was referred to as “aniline group-containing PVA”).
).

Example 1 [Preparation of Two-Component Adhesive Composition and Adhesion Test] (1) One of the aniline group-containing PVAs obtained in Synthesis Example 1
A first liquid was prepared by blending 50 parts of calcium carbonate (trade name: P-30, manufactured by Toyo Fine Chemical Co., Ltd.) with 100 parts of a 0% aqueous solution. (2) On the other hand, a 15% aqueous solution of ammonium persulfate
It was prepared as a liquid. (3) The first liquid and the second liquid prepared or prepared as described above were combined to obtain a two-part adhesive composition. (4) Five pairs of adherends each consisting of two test pieces (birch material, mosaic pattern) of length x width x thickness = 25 x 25 x 10 mm were prepared for each adhesive composition. did. The first liquid prepared in the above (1) was applied to the adhesive surface of one test piece of the pair of adherends (applied amount: about 200 g / m ² ), and the above (2) was applied to the adhesive surface of the other test piece. 2) was applied (applying amount: about 50 g / m ² ), and both application surfaces were bonded together and pressed (pressing pressure: about 10 kg / cm ² ). Next, each pair of adherends was pressed for the time shown in Table 1, decompressed after each press time, and cured for 5 minutes or 24 hours. -6862
The adhesive strength (compression shear bond strength) was measured by a method according to the “test method for compressive shear bond strength of adhesive”, and an average value of 5 pairs was taken. In addition, in the above-described test of the adhesive strength after curing for 24 hours, the ratio [destruction rate (%)] in which the adhesive did not peel off on the adhesive-coated surface of the adherend but occurred in the part of the adherend was simultaneously measured. The values are shown in parentheses in the following table. The higher the value of the breaking ratio, the higher the adhesive strength of the adhesive composition. The above-mentioned bonding operation and test were all performed in an atmosphere at 20 ° C. The results are shown in Table 1 below.

Comparative Example 1 [Adhesion Test] An adhesion test similar to that of Example 1 was performed, except that the adhesion was performed using only the first liquid without using the ammonium persulfate aqueous solution of the second liquid. And the fracture rate of the adherend was determined. Table 1 shows the results.

<< Comparative Example 2 >> [Preparation of Two-Component Adhesive Composition and Adhesion Test] (1) Unmodified PVA containing no amino group bonded to phenyl group (polymerization degree: 1110, saponification degree: 98.5%) A two-part adhesive composition was prepared in the same manner as in Example 1 except that the adhesive was used, and an adhesion test was performed using the same to measure the adhesive strength and the destruction rate of the adherend in the same manner as in Example 1. I asked. Table 1 shows the results.

[0047]

[Table 1]

1) Contents of PVA aqueous solution: 10% of aniline group-containing PVA obtained in Synthesis Example 1
Aqueous solution: unmodified PVA (degree of polymerization 1110, degree of saponification 98.5)
2) Curing time after compression release 3) Compressive shear strength (adhesive strength) shows the average value of five pairs of test pieces. The numerical value in parentheses after the numerical value of the compressive shear strength after curing for 24 hours indicates the destruction rate (%) of the adherend generated when the test of the compressive shear strength was performed. 4) 15% ammonium persulfate aqueous solution

From the results in Table 1 above, it can be seen that the aniline group-containing P
Two-component separation coating method using a two-component adhesive composition in which an aqueous liquid [liquid (a)] prepared using VA is a first liquid and an aqueous solution of a water-soluble oxidizing agent is a second liquid. In the case of Example 1 in which the bonding was performed according to Example 1, after 1 minute of the pressing time, the bonding strength was already considerably high, and the bonded adhered material pair did not peel off, and the bonding could be performed with good workability. thing,
In addition, after curing for 24 hours, it shows an extremely high adhesive strength, indicating that it has good adhesive performance. On the other hand, in the case of Comparative Example 1 in which the bonding was performed using only the aqueous liquid [Liquid 1 (a)] prepared using the aniline group-containing PVA, and in the case of Comparative Example 1 in which no amino group bonded to the phenyl group was contained. In the case of Comparative Example 2 in which the aqueous liquid prepared using the modified PVA is used as the first liquid and the two-part adhesive composition using the aqueous oxidizing agent aqueous solution as the second liquid is used for bonding,
Even after 5 minutes of pressing, the adhesive strength is low or only a certain degree of adhesive strength is developed, and even after curing for 24 hours, the adhesive strength is significantly lower than that of Example 1. You can see that there is.

Example 2 [Preparation of Two-Component Adhesive Composition and Adhesion Test] Calcium carbonate (manufactured by Toyo Fine Chemical; trade name: 100 parts of a 10% aqueous solution of aniline group-containing PVA obtained in Synthesis Example 1) P-30) was mixed with 50 parts to prepare a first liquid. On the other hand, a 15% aqueous hydrogen peroxide solution was prepared as a second liquid. Using the first liquid and the second liquid prepared or prepared as described above, an adhesion test was performed in the same manner as in Example 1 to measure an adhesion strength, and a destruction rate of an adherend was determined. Table 2 shows the results.

<< Comparative Example 3 >> [Preparation of Two-Part Adhesive Composition and Adhesion Test] Except for preparing the first liquid using the unmodified PVA containing no amino group bonded to the phenyl group of Comparative Example 2 Prepared a two-part adhesive composition in the same manner as in Example 2, and performed an adhesion test using the same to measure the adhesive strength and determine the breaking rate of the adherend in the same manner as in Example 1. . Table 2 shows the results.

[0052]

[Table 2]

1) Contents of PVA aqueous solution: 10% of aniline group-containing PVA obtained in Synthesis Example 1
Aqueous solution: unmodified PVA (degree of polymerization 1110, degree of saponification 98.5)
2) Curing time after compression release 3) Compressive shear strength (adhesive strength) shows the average value of five pairs of test pieces. The numerical value in parentheses after the numerical value of the compressive shear strength after curing for 24 hours indicates the destruction rate (%) of the adherend generated when the test of the compressive shear strength was performed. 4) 15% hydrogen peroxide aqueous solution

From the results in Table 2 above, it can be seen that the aniline group-containing P
An aqueous liquid prepared using VA was used as a first liquid, and a liquid containing hydrogen peroxide was used as a second liquid, using a two-part adhesive composition.
In the case of Example 2 in which the bonding was performed by the two-liquid separation coating method, the bonding strength was already high after one minute of the pressing time, and the peeling between the bonded adherends did not occur. It can be seen that bonding can be carried out, and after curing for 24 hours, it shows extremely high bonding strength and has good bonding performance. On the other hand, an aqueous liquid prepared using unmodified PVA containing no amino group bonded to a phenyl group was used as a first liquid, and a liquid containing hydrogen peroxide was used as a second liquid.
In the case of Comparative Example 3 in which bonding was performed using a two-part adhesive composition as a liquid, only a certain degree of bonding strength was gradually developed after a pressing time of 3 minutes, and curing was performed for 24 hours. It can be seen that the adhesive strength is much lower than in Example 2 even later.

Example 3 [Preparation of Two-Part Adhesive Composition and Adhesion Test] 100 parts of a 10% aqueous solution of aniline group-containing PVA obtained in Synthesis Example 1 was mixed with calcium carbonate (Toyo Fine Chemical; product) No. P-30) was mixed with 50 parts to prepare a first liquid. On the other hand, a 15% ammonium persulfate aqueous solution 10
10 parts of a hydrophilic polyepoxy compound (ethylene glycol diglycidyl ether) is added to
A liquid was prepared. Using the first liquid and the second liquid prepared as described above, an adhesion test was performed in the same manner as in Example 1 to measure the adhesion strength, and the destruction rate of the adherend was determined. Table 3 shows the results.

Example 4 [Preparation of Two-Part Adhesive Composition and Adhesion Test] 100 parts of a 10% aqueous solution of aniline group-containing PVA obtained in Synthesis Example 1 was treated with calcium carbonate (manufactured by Toyo Fine Chemical; product). No. P-30) was mixed with 50 parts to prepare a first liquid. On the other hand, a 15% ammonium persulfate aqueous solution 10
A second liquid was prepared by mixing 10 parts of a 15% aqueous glyoxal solution with 0 parts. The first liquid prepared above and the second liquid
Using the liquid, an adhesion test was performed in the same manner as in Example 1 to measure the adhesion strength, and the fracture rate of the adherend was determined. Table 3 shows the results.

<< Comparative Example 4 >> [Preparation of Two-Part Adhesive Composition and Adhesion Test] Except for preparing the first liquid using the unmodified PVA containing no amino group bonded to the phenyl group of Comparative Example 2, Example 3
A two-part adhesive composition was prepared in the same manner as described above, and an adhesive test was performed using the two-part adhesive composition in the same manner as in Example 1 to measure the adhesive strength and to determine the breaking rate of the adherend. Table 3 shows the results.
Shown in

<< Comparative Example 5 >> [Preparation of Two-Part Adhesive Composition and Adhesion Test] Except that the first liquid was prepared using the unmodified PVA containing no amino group bonded to the phenyl group of Comparative Example 2, Example 4
A two-part adhesive composition was prepared in the same manner as described above, and an adhesive test was performed using the two-part adhesive composition in the same manner as in Example 1 to measure the adhesive strength and to determine the breaking rate of the adherend. Table 3 shows the results.
Shown in

[0059]

[Table 3]

1) Contents of PVA aqueous solution: 10% of aniline group-containing PVA obtained in Synthesis Example 1
Aqueous solution: unmodified PVA (degree of polymerization 1110, degree of saponification 98.5)
2) Curing time after compression release 3) Compressive shear strength (adhesive strength) shows the average value of five pairs of test pieces. The numerical value in parentheses after the numerical value of the compressive shear strength after curing for 24 hours indicates the destruction rate (%) of the adherend generated when the test of the compressive shear strength was performed. 4) A: 15% aqueous hydrogen peroxide solution 5) B: ethylene glycol diglycidyl ether 6) C: 15% aqueous glyoxal solution

From the results in Table 3 above, it can be seen that the aniline group-containing P
An aqueous liquid prepared using VA is used as a first liquid, and a liquid containing a polyvalent epoxy compound or an aldehyde compound together with a water-soluble oxidizing agent is used as a second liquid.
In the case of Examples 3 and 4 in which the bonding was performed by the two-liquid separation coating method, the bonding material (a pair of test pieces) which had already exhibited a considerably high bonding strength after one minute of the pressing time and did not peel was not generated. Thus, it can be seen that bonding can be carried out with good workability, and that after having been cured for 24 hours, extremely high bonding strength is exhibited and good bonding performance is obtained. In contrast, an aqueous liquid prepared using unmodified PVA that does not contain an amino group bonded to a phenyl group is referred to as a first liquid, and a liquid containing a polyvalent epoxy compound or an aldehyde compound together with a water-soluble oxidizing agent is referred to as a second liquid. Using a two-part adhesive composition
In the case of Comparative Examples 4 and 5 in which adhesion was performed by the two-liquid separation coating method, only a certain degree of adhesive strength was gradually developed after 5 minutes of pressing, and even after curing for 24 hours, Examples 3 to 5 were used. It can be seen that the adhesive strength is significantly lower than that of No. 4.

Example 5 [Preparation of Two-Part Adhesive Composition and Adhesion Test] A polyvalent epoxy compound (ethylene glycol) was added to 100 parts of a 10% aqueous solution of aniline group-containing PVA obtained in Synthesis Example 1. 10 parts of diglycidyl ether) and 5 parts of calcium carbonate (trade name: P-30, manufactured by Toyo Fine Chemical)
The first liquid was prepared by mixing 0 parts. On the other hand, a 15% aqueous solution of ammonium persulfate was prepared as a second liquid. Using the first liquid and the second liquid prepared or prepared above, an adhesion test was performed in the same manner as in Example 1 to measure the adhesion strength, and
The fracture rate of the adherend was determined. Table 4 shows the results.

Comparative Example 6 [Preparation of Two-Part Adhesive Composition and Adhesion Test] A first liquid was prepared using the unmodified PVA containing no amino group bonded to the phenyl group prepared in Comparative Example 2. Except for the above, a two-part adhesive composition was prepared in the same manner as in Example 4, an adhesion test was performed in the same manner as in Example 1, the adhesive strength was measured, and the destruction rate of the adherend was determined. Table 4 shows the results.

[0064]

[Table 4]

1) Contents of PVA aqueous solution: 10% of aniline group-containing PVA obtained in Synthesis Example 1
Aqueous solution: unmodified PVA (degree of polymerization 1110, degree of saponification 98.5)
2) Curing time after compression release 3) Compressive shear strength (adhesive strength) shows the average value of five pairs of test pieces. The numerical value in parentheses after the numerical value of the compressive shear strength after curing for 24 hours indicates the destruction rate (%) of the adherend generated when the test of the compressive shear strength was performed. 4) B: Ethylene glycol diglycidyl ether 5) 15% ammonium persulfate aqueous solution

From the results in Table 4 above, it can be seen that the aniline group-containing P
An aqueous liquid prepared using VA and a polyepoxy compound is used as a first liquid, and an aqueous solution of a water-soluble oxidizing agent is used as a second liquid 2
In the case of Example 5 in which the liquid type adhesive composition was used to perform bonding by the two-liquid separation coating method, the bonded material (1 pair) which exhibited a considerably high bonding strength already 1 minute after the pressing time and was bonded. It can be seen that the peeling of the test piece does not occur and the bonding can be performed with good workability, and further, after curing for 24 hours, it shows extremely high bonding strength and has good bonding performance. On the other hand, adhesion was performed using an aqueous liquid containing unmodified PVA containing no amino group bonded to a phenyl group and a polyvalent epoxy compound as a first liquid, and a liquid containing a water-soluble oxidizing agent as a second liquid. In the case of Comparative Example 6, only a certain degree of adhesive strength was gradually developed after the pressing time of 5 minutes, and even after curing for 24 hours, the adhesive strength was significantly lower than that of Example 5. You can see that there is.

Example 6 [Preparation of Two-Part Adhesive Composition and Adhesion Test] 100 parts of a 10% aqueous solution of aniline group-containing PVA obtained in Synthesis Example 1 was mixed with calcium carbonate (manufactured by Toyo Fine Chemical; 50 parts of an organic polymer aqueous emulsion (trade name: P-30) and 100 parts of an organic polymer aqueous emulsion (ethylene-vinyl acetate copolymer aqueous emulsion; solid content concentration: 55%; "OM-4200" manufactured by Kuraray Co., Ltd.) A liquid was prepared. On the other hand, a 15% aqueous solution of ammonium persulfate was prepared as a second liquid. Using the first liquid and the second liquid prepared or prepared as described above, an adhesion test was performed in the same manner as in Example 1 to measure the adhesion strength, and the destruction rate of the adherend was determined. The results are shown in Table 5 below.

Example 7 [Adhesion Test] Example 6 except that an aqueous hydrogen peroxide solution was used as the second liquid.
In the same manner as in the above, an adhesion test was performed to measure the adhesion strength, and the destruction rate of the adherend was determined. The results are shown in Table 5 below.

Comparative Example 7 [Adhesion Test] An adhesion test was carried out in the same manner as in Example 6, except that the first solution was used without using the aqueous solution of ammonium persulfate as the second solution. Then, the breaking rate of the adherend was determined.
The results are shown in Table 5 below.

Comparative Example 8 [Preparation of Two-Component Adhesive Composition and Adhesion Test] Unmodified PV not containing an amino group bonded to a phenyl group
A (100 parts of 10% aqueous solution of polymerization degree 1110, saponification degree 98.5%), 50 parts of calcium carbonate (manufactured by Toyo Fine Chemical; trade name: P-30) and 50 parts of organic polymer aqueous emulsion (ethylene-vinyl acetate) A first liquid was prepared by mixing 100 parts of a copolymer aqueous emulsion; a solid content concentration of 55%; "OM-4200" manufactured by Kuraray Co., Ltd.). On the other hand, a 15% aqueous solution of ammonium persulfate was prepared as a second liquid. Using the first liquid and the second liquid prepared or prepared as described above, an adhesion test was performed in the same manner as in Example 1 to measure the adhesion strength, and the destruction rate of the adherend was determined. The results are shown in Table 5 below.

[0071]

[Table 5]

1) Contents of PVA aqueous solution: 10% of aniline group-containing PVA obtained in Synthesis Example 1
Aqueous solution: unmodified PVA (degree of polymerization 1110, degree of saponification 98.5)
2) Content of polymer emulsion D: Ethylene-vinyl acetate copolymer emulsion ("OM-4200" manufactured by Kuraray Co., Ltd.) 3) Curing time after pressing and releasing 4) Compressive shear strength (Adhesive strength) shows the average value of five pairs of test pieces. The numerical value in parentheses after the numerical value of the compressive shear strength after curing for 24 hours indicates the destruction rate (%) of the adherend generated when the test of the compressive shear strength was performed. 5) 15% ammonium persulfate aqueous solution

From the results in Table 5 above, it can be seen that the aniline group-containing P
Adhesion is carried out by a two-component separation coating method using a two-component adhesive composition in which an aqueous solution mainly composed of VA and an organic polymer aqueous emulsion is used as a first liquid, and an aqueous solution of a water-soluble oxidizing agent is used as a second liquid. In the case of Examples 6 to 7, the adhesive strength was already considerably high after one minute of the pressing time, and the adhered material (one pair of test pieces) was not peeled off. Can be carried out, and after curing for 24 hours, it shows an extremely high adhesive strength and has good adhesive performance. In contrast, Comparative Example 7 in which adhesion was performed using only an aqueous solution mainly composed of an aniline group-containing PVA and an organic polymer aqueous emulsion, and unmodified P which did not contain an amino group bonded to a phenyl group.
In the case of Comparative Example 8 in which bonding is performed using an aqueous liquid mainly composed of VA and an organic polymer aqueous emulsion as a first liquid and a liquid containing a water-soluble oxidizing agent as a second liquid, after pressing for 5 minutes, Only a certain degree of adhesive strength is developed, and even after curing for 24 hours, Examples 6-7
It can be seen that the adhesive strength is significantly lower than that of the above.

[0074]

The two-part adhesive composition of the present invention reacts and cures at room temperature in a short time when the first and second parts are brought into contact with each other to exhibit high initial adhesive strength. Therefore, when bonding is performed using the two-part adhesive composition of the present invention, the bonding operation can be performed with good workability and processability and at low energy cost. In particular, using the two-component adhesive composition of the present invention, the first liquid is applied to one of the adherends, the second liquid is applied to the other adherent, and both adherent surfaces are brought into close contact with each other. When bonding is performed by a two-liquid separation coating method, the bonding operation can be performed extremely smoothly due to its fast curing property. And the adherend obtained using the two-part adhesive composition of the present invention has a high final adhesive strength,
No troubles such as peeling of the bonded part occur. Furthermore, the two-part adhesive composition of the present invention is excellent in storage stability and mechanical stability, hardly causes sedimentation, separation, aggregation and the like of the components even when allowed to stand, and furthermore, during transportation and handling. Even when subjected to the action of rocking, stirring, or the like from the outside at the time, the components are unlikely to settle, separate, or aggregate, and the adhesive performance can be favorably maintained. Two-part adhesive composition having the property of being capable of being used, especially two-part adhesives suitable for two-part separate coating. Therefore, the two-part adhesive composition of the present invention makes use of the various excellent properties described above to produce various types of wood. Materials, for example, wood, materials such as chipboard, hardboard, woody materials such as slate board, silicacal board; melamine resin decorative material,
Bakelite, other plastic materials; paper materials such as corrugated paperboard and kraft paper; fabrics and other textiles; can be effectively used for bonding inorganic boards and the like;
It is particularly suitable for bonding wood.

Claims (6)

[Claims] 1. A two-part adhesive composition comprising a first liquid comprising an aqueous liquid containing a vinyl alcohol polymer having an amino group bonded to a phenyl group and a second liquid containing a water-soluble oxidizing agent. 2. The two-component adhesive composition according to claim 1, wherein the first liquid is an aqueous liquid comprising a vinyl alcohol polymer having an amino group bonded to a phenyl group and an organic polymer aqueous emulsion. 3. The two-part adhesive according to claim 1, wherein the vinyl alcohol polymer having an amino group bonded to a phenyl group is a vinyl alcohol polymer having the following structural unit. Composition. Embedded image Embedded image (Where R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a hydrocarbon group which may have a substituent having 8 or less carbon atoms, and A is a divalent hydrocarbon group Or a nitrogen atom,
It represents a divalent hydrocarbon group containing at least one oxygen atom or sulfur atom, S represents a sulfur atom, and X represents a monovalent group containing an amino group bonded to a phenyl group. ) 4. The second liquid is a liquid containing a water-soluble oxidizing agent, and at least one of the first liquid and the second liquid is at least one compound selected from a polyepoxy compound, an aldehyde compound and a polyisocyanate compound. The two-part adhesive composition according to claim 1, further comprising: 5. The two-part adhesive composition according to claim 1, which is a two-part separation coating type adhesive composition. 6. The method according to claim 1, wherein
The first liquid of the liquid adhesive composition is applied to the first adherend surface, the second liquid is applied to the second adherent surface, and the two adhered surfaces are brought into close contact with each other for adhesion. And the bonding method.